Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/02—Macromolecular compounds
  • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B26/06—Acrylates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/04—Apparatus for manufacture or treatment
  • H10P72/0441—Apparatus for sealing, encapsulating, glassing, decapsulating or the like
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

• This invention relates to the manufacture of acrylic sheet or slabs, that is sheets or slabs of polymethylmethacrylate (“PMMA”), of the type usable in or designed for architectural uses such as kitchen countertops and more complex shapes.
• the sheets ⁇ r slabs contain significant amounts of flame retardant minerals, typically alumina trihydrate, and almost always have colorants in them, frequently in imitation of natural minerals such as onyx, marble or similar synthetic appearing solid color or patterned types having no visibly distinguishable particles.
• This invention describes a sheet that can be heated and bent at a sharp 90° angle and/or that can be heated and vacuum formed into bent at a sharp 90° angle and/or that can be heated and vacuum formed into
• the sheets or slabs of this invention display specific physical and other properties
• such a part can only be produced by casting it in a mold cavity under
• thermoforming operation that is, the sheet is heated and then pulled by vacuum
• Such a mold can be shaped as a vanity top, with one 90° back splash
• the part can be installed directly in place, without
• curvature specified by the Corian literature of which we are aware is 3.0 inches.
• PMMA polymethylmethacrylate
• alumina trihydrate (“ATH) is now widely used as a filler in various resinuous products.
• MMA polymerizable methyl methacrylate
• polishing be protected against flammability, and have good temperature resistance in spite of being thermoformable.
• thermobending of solid surface sheets since the prior art products were generally
• FIG. 1A is a more or less hypothetical illustration of a prior art bending of
• FIG. B is a similar idealized illustration of the bending of a sheet of the
• the present invention addresses the making of mineral filled PMMA
• thermoforming temperature low enough to avoid any
• thermoplastic materials have a Flame Spread Index, by the ASTM E-84 Tunnel Test, lower
• Our invention provides for the stability of the suspension of alumina
• ATH in the entire composition 20-60% by weight, preferably 25-
• Thixotropic agent preferably fumed silica
• Crosslinking agent as % weight of the total monomers content:
• Chain-transfer agent as % weight of the total monomers content as
• MW W and MW n should be similar to that obtained by n-dodecyl
• dyes and pigments may be any organic compound.
• dyes and pigments may be any organic compound.
• ingredients may be used as are known in the art.
• particles of various compositions and colors ranging from about 150 to 500 microns — that is, they will pass through a sieve having openings of 500 microns
• retardants such as ATH, for example, or synthetic resin or other fillers.
• PMMA as used herein is polymethylmethacrylate having a (weight
• cross linked polymer chains in order to remain soluble in MMA. It is typically
• MMA is methyl methacrylate.
• the syrup is described herein as
• chain terminator, initiator, and thixotropic agent are also present in the amounts indicated herein as well as variable amounts of dyes and/or pigments; in addition,
• MMA should be understood possibly to include such additional materials.
• Alumina trihydrate is well known in the art of synthetic mineral
• the particulate size may vary widely. As noted above, the particulate size may vary widely.
• the ATH may vary from about 20% to about 60%
• Our invention contemplates a solid surface material in which may be seen
• grains or particles are individually visibly discemable.
• crosslinking agents di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslinking agents, di-functional or tri-functional, may be any number of crosslink
• crosslinkers examples include ethylene glycol dimethyl acrylate,
• propylene dimethyl acrylate polyethylene-glycol diemethylacrylate
• ethylene glycol dimethacrylate is
• crosslinking agents are maintained in concentrations of greater
• the MMA in the syrup or, as a component of the finished product, based on the
• crosslinked polymer Most preferably, the content is 6.0 > x > 1.0.
• thermoformability
• Chain terminators or chain-transfer agents such as octyl mercaptan, iso- dodecyl mercaptan, thiurams, dithiocarbarumates, dipentene dimercaptan, 2-
• chain terminators or chain-transfer agents are used
• thixotropic agents we use are shown herein to be particularly suited for
• fumed silica is hydrophilic since it has an abundance of
• the final viscosity of the suspension will be higher than when using the
• the amount of fumed silica is selected so that
• the preferred method of obtaining a desired viscosity is the following:
• step A including an amount of fumed silica and measure the
• step B Repeat step B to bring the viscosity to a level between 1,000 and
• centipoise preferably between 2,000 and 5,000 centipoise.
• crosslinker chain terminator, fumed silica, and PMMA prepolymer are important
• ingredients has a tendency to distort the visual or decorative pattern; accordingly,
• Figure IB illustrates the achievable curvature of a sheet of the present
• thermoformability which is a primary
• the test consists of clamping a flat test specimen
• one-inch radius is lowered at a rate of five inches per minute regardless of the
• a load cell generates a signal representing the
• This test may be referred to herein as TP-0085.
• a syrup was made by partial polymerization of MMA to obtain a viscosity of 3
• the mixture of ingredients was first agitated under vacuum for 15 minutes, to
• Table 2 shows the combinations of chain transfer agent and crosslinker
• the first group of data (PL-8, PL-11, PL-12, PL-14, PL-16, PL-19, PL-24,
• PL-25, PL-28 listed in Table 2 represents compositions that were thermoformed under vacuum to a much greater extent than compositions from the known art.
• the second group of data (PL- 10, PL-13, PL-20, PL-23) represents
• the third group of data (PL- 12, PL-22, PL-27) represents formulations

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Road Signs Or Road Markings (AREA)
• Polymerisation Methods In General (AREA)
• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

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• 1997
  • 1997-07-07 US US08/888,958 patent/US5985972A/en not_active Expired - Lifetime
• 1998
  • 1998-06-26 AT AT98932896T patent/ATE302811T1/de not_active IP Right Cessation
  • 1998-06-26 EP EP98932896A patent/EP0932638B1/fr not_active Expired - Lifetime
  • 1998-06-26 WO PCT/US1998/013334 patent/WO1999002582A1/fr not_active Ceased
  • 1998-06-26 JP JP11508701A patent/JP2001501253A/ja not_active Ceased
  • 1998-06-26 DE DE69831309T patent/DE69831309T2/de not_active Expired - Fee Related
  • 1998-06-26 CA CA002265496A patent/CA2265496C/fr not_active Expired - Fee Related
  • 1998-06-26 ES ES98932896T patent/ES2248910T3/es not_active Expired - Lifetime
• 1999
  • 1999-03-10 US US09/266,185 patent/US6177499B1/en not_active Expired - Lifetime
• 2000
  • 2000-06-08 US US09/590,348 patent/US6562927B1/en not_active Expired - Lifetime

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